Foods and flavor use of 1-(3,3-dimethyl-2-norbornyl-2-propanone

ABSTRACT

Processes and compositions are described for the use in foodstuff, chewing gum, toothpaste and medicinal product flavor and aroma and perfume aroma augmenting, enhancing, modifying and imparting compositions and as foodstuff, chewing gum, toothpaste, medicinal product, perfume and perfumed article aroma imparting materials of 1-(3,3-dimethyl-2-norbornyl)-2-propanone (hereinafter referred to as the &#34;norbornylpropanone derivative&#34;) having the structure:   &lt;IMAGE&gt; (which structure is intended to cover both the &#34;endo&#34; and the &#34;exo&#34; isomers thereof). Addition of the said &#34;norbornylpropanone derivative&#34; to consumable materials is indicated to produce:

BACKGROUND OF THE INVENTION

The present invention relates to1-(3,3-dimethyl-2-norbornyl)-2-propanone and compositions using said"norbornylpropanone derivative" to augment or enhance the flavor and/oraroma of consumable materials or impart flavor and/or aroma toconsumable materials.

There has been considerable work performed relating to substances whichcan be used to impart (modify, augment or enhance) flavors andfragrances to (or in) various consumable materials. These substances areused to diminish the use of natural materials, some of which may be inshort supply and to provide more uniform properties in the finishedproduct.

Fruity/berry, pine needle-like aromas with sweet, fruity/berry,blueberry-like, pine needle-like and pine balsam flavor characteristicsare particularly desirable for many uses in foodstuff flavors, chewinggum flavors, toothpaste flavors and medicinal product flavors.

Sweet, berry, woody, piney, mint aroma notes with a damascenone-likecharacter and buttery and minty nuances are desirable in several typesof perfume compositions, perfumed articles and colognes.

U.S. Pat. No. 3,852,358 issued on Dec. 3, 1974 discloses a process forproducing 2-acetyl-3,3-dimethyl-5-norbornene in both the exo and endoforms which have uses in perfumery and other fragrance applications.These compounds have the structures: ##STR2## These compounds, producedby reaction of cyclopentadiene with mesityl oxide, are startingmaterials for producing a number of the compounds of our invention.However, the compounds of our invention have unexpected, unobvious andadvantageous properties when compared with the2-acetyl-3,3-dimethyl-5-norbornene of U.S. Pat. No. 3,852,358.

U.S. Pat. No. 3,942,761 discloses the use in perfumery of4(2'-norbornyl)-2-butanones having the structure: ##STR3## wherein R₁ ishydrogen or methyl and R is hydrogen or lower alkyl containing from 1 to8 carbon atoms. Such compounds have structures which are different inkind from the structures of the compounds of our invention. Alsodisclosed as intermediates for producing the foregoing compounds arecompounds having the generic structure: ##STR4## wherein the dotted lineis a carbon-carbon single bond or a carbon-carbon double bond. Inaddition, the following reaction sequence is set forth therein: ##STR5##

Arctander, "Perfume and Flavor Chemicals," 1969, Vol. 1, discloses theuse in perfume compositions and in foodstuff flavors of "fenchone,""fenchyl alcohol," "camphene carbinol," and "camphene carbinyl acetate,"thus:

(i) "1385: FENCHONE

laevo-Fenchone. (dextro- is known but less common as a fragrancematerial).

1,3,3-Trimethyl-2-norbornanone.

1,3,3,-Trimethyl bicyclo-1,2,2-heptanone-2. ##STR6## Warm-camphoraceous,powerful and diffusive, basically sweet odor. Warm, somewhat burning andbitter taste with a medicinal note.

This ketone finds some use as a masking odor in industrial fragrances.It is also used in the reconstruction of Fennel oil and a few otheressential oils.

In spite of its rather unpleasant taste, it is used in various Berrycomplex flavors, in Spice complexes and in certain types of Liquerflavoring.

The concentration used is about 0.1 to 5 ppm in the finished product".

(ii) "1387: FENCHYL ALCOHOL

1,3,3-trimethyl-2-norbornanol.

1,3,3-Trimethyl bicyclo-1,2,2-heptanol-2.

2-Fenchanol.

Fenchol. ##STR7## Powerful and diffusive, Camphor-like, but sweeter andmore Citrus-like almost Lime-like odor with more or less of anearthy-dry character, according to the composition and isomer-ratio.

The taste is somewhat bitter-Lime-like, camphoraceous and slightlywoody-musty.

This interesting alcohol (or mixed alcohols) finds use in perfumecompositions ranging from woody or herbaceous to Citrus-Lime and evencertain floral types. It produces power and "lift" to floral fragrances,and solid background to Lime and other Citrus bases, having theadvantage over the Terpenes in being very stable in soap.

Fenchyl alcohol is also used in flavor compositions such as Strawberryand other berries, Lime and Spice, etc.

The concentration is normally low, e.g. 0.2 up to 5 ppm in the finishedproduct".

(iii) "1028: 3,3-DIMETHYL-Δ², beta-NORBORNANE-2-ETHANOL "Camphenecarbinol". ##STR8## Sweet-camphoraceous, warm and soft odor with a woodyundertone. Upon standing it may develop an odor resembling that ofCelluloid.

Although rarely offered commercially, this chemical could find some usein perfume compositions of the woody, Oriental and orrisy type, in newvariations of Pine fragrances, and in various soap and detergentperfumes".

(iv) "1029: 3,3-DIMETHYL-Δ² -beta-NORBORNANE-2-ETHYL-ACETATE

"camphene carbinyl acetate". ##STR9## Mild and sweet-woody odor with afloral-piney undertone. The commercial products are probably notwell-defined single chemicals, and great variations in odor have beenobserved.

This ester has been developed in line with the research on Sandalwoodtype odors. The parent alcohol "Camphene carbinol" was once considereduseful as a Sandalwood type material, but it has found more use as asweetening and enriching ingredient in sophisticated Pine fragrances.The title ester finds limited use in perfume compositions of woodycharacter, Fougeres, Pine fragrances, etc. and it blends very well withthe Cyclohexanol derivatives, Ionones, iso-Bornylacetate, Nitromusks,etc.".

U.S. Pat. No. 3,928,456 discloses monocyclic compounds having thegeneric structure: ##STR10## containing one double bond in position 2'-or 3'- of the acyl side-chain and either one double bond in position 1-or 2-(as shown in the above formula, the double bond in the 2 positioncan be either in the cycle or the side chain), or two conjugated doublebonds in positions 1- and 3- of the cycle, the double bonds beingrepresented by dotted lines, and wherein n is 0 or 1, R¹, R² and R³represent hydrogen or one of them a lower alkyl radical, such as methylor ethyl, and the others hydrogen, and R⁴, R⁵, R⁶ and R⁷ representhydrogen or one of them a lower alkyl radical, such as methyl or ethyl,and the others hydrogen, as being useful in perfumery and food flavorsand also flavors, beverages, animal feeds and tobaccos. Specificallydisclosed in this patent is a compound having the structure: ##STR11##

U.S. Application for Letters Pat. Ser. No. 551,030, filed on Feb. 19,1975, and now U.S. Pat. No. 4,000,050 discloses, interalia, perfumeryuses of compounds having the structures: ##STR12## wherein one of thedashed lines is a carbon-carbon bond and each of the wavy lines is acarbon-carbon single bond, one of the carbon-carbon single bondsrepresented by the wavy line being epimeric with respect to the other ofthe carbon-carbon single bonds represented by the wavy line.

In addition, various processes and compounds relating to the synthesisof synthetic sandalwood oil components are described in the followingU.S. Patents:

(i) Perfume Compounds And Process For Preparing Same U.S. Pat. No.3,673,261 issued June 27, 1972:

Compounds: ##STR13##2-methylene-3-exo(trans-4'-methyl-5'-hydroxypent-3'-enyl)bicyclo[2.2.1]-heptanetrans-3-Normethyl-beta-santalol##STR14##2-methylene-3-exo(cis-4'-methyl-5'-hydroxypent-3'-enyl)bicyclo[2.2.1]-heptanecis-3-normethyl-betasantalol ##STR15##2-methylene-3-exo(4'-methyl-5'-hydroxypentyl)bicyclo[2.2.1]heptane-3-normethyldihydro-beta-santalol

(ii) Dihydro-beta-santalol and Processes For PreparingDihydro-beta-Santalol From3-Endo-Methyl-3-Exo(4'-Methyl-5'-Hydroxyphenyl) Norcamphor -- U.S. Pat.No. 3,673,263 issued June 27, 1972: ##STR16## dihydro-beta-santalol(iii) Process for Preparing Beta-Santalol From 3-Methylnorcamphor --U.S. Pat. No. 3,662,008 issued May 9, 1972: ##STR17##endo-3-methyl-exo-3(cis-5'-hydroxy-4'-methylpent-3'-enyl)-2-methylenebicyclo-(2.2.1)heptane ##STR18##endo-3-methyl-exo-3(trans-5'-hydroxy-4'-methylpent-3'-enyl)-2-methylenebicyclo(2.2.1)heptane

(iv) Process For Preparing Dihydro-Beta-Santalol From3-Endo-Methyl-3-Exo(4'-Methyl-5'-Hydroxypentyl) Norcamphor -- U.S. Pat.No. 3,673,266, issued June 27, 1972: ##STR19## dihydro-beta-santalol

None of the compounds disclosed in either U.S. Pat. No. 3,928,456 orU.S. Application for Letters Pat. Ser. No. 551,030, filed Feb. 19, 1975,and now U.S. Pat. No. 4,000,050 have properties even closely similar tothe properties of the "nonbornylpropanone derivative" of the instantapplication.

Chem. Abstracts, Vol. 84, 73728n (abstract of Karaev, et al,Zh.Org.Khim. 1975, 11(12), 2622) discloses preparation of the compound:##STR20##

Klein and Rojahn, Chem.Abstracts, Vol. 84, 90327y (1976) discloses theuse of compounds having the generic structure: ##STR21## (wherein thedashed line is a single or double bond) as an intermediate in thepreparation of beta-santalol; but no organoleptic properties of thesenonbornane derivatives are disclosed.

U.S. Pat. No. 3,748,344, issued on July 24, 1973, discloses thatchemical compounds characterized by the structural formula: ##STR22##wherein the dashed line represents the presence of a single or a doublebond wherein R₁ ', R₂ ', R₃ ', and R₄ ' each represent hydrogen or lowermethyl and R₅ ' represents hydrogen or lower alkyl and R₆ ' represents apolymethylene radical of from 2 to 4 carbon atoms which is unsubstitutedor substituted with lower alkyl, which "as a whole exhibits acharacteristic, pleasant, strong and long lasting aroma which is highlyuseful in the preparation of fragrance compositions and perfumeproducts". Various notes are described such as green, cuminic, walnut,raw potato, earthy, camphoraceous, civet, walnut bark, neroli, anise,vegetable, menthone, animal, minty, eucalyptol, cucumber, pine andfecal.

In addition, U.S. Pat. No. 3,748,344 discloses as chemical intermediatesfor preparing the above ketal, a compound having the generic structure:##STR23## wherein R₁ ', R₂ ', R₃ ', R₄ ' and R₅ ' have the same meaningas defined above.

However, the specific compound of our invention is not set forth in U.S.Pat. No. 3,748,344.

No prediction of the organoleptic properties of the compound of theinstant invention can be made by a study of the disclosure of U.S. Pat.No. 3,748,344.

Chemical Abstracts, Vol. 71, 49664z (abstract of Sadykh-Zade, et al(U.S.S.R.) Dokl. Akad. Nauk Azerb. SSR 1968, 24(11), 38-41) disclosesthe synthesis of exo and endo forms of the compounds having thestructures: ##STR24##

Chemical Abstracts, Vol. 81, 135512m (abstract of Akhmedov, I.M., et al(Inst. Georg. Fiz. Khim., Baku, U.S.S.R.). Dokl. Akad. Nauk Az. SSR1974, 30(4), 18-21) discloses the synthesis of the compound having thestructure: ##STR25##

None of the Chemical Abstracts references discloses compounds which havea close structural relationship to the compound of the instantinvention. In any event, the organoleptic properties of the compounds ofthe Chemical Abstract references are different in kind from those of thecompound of the instant invention.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is the NMR spectrum for the "norbornylpropanone derivative" ofour invention produced in Example I.

FIG. 2 is the Infrared spectrum for the "norbornyl-propanone derivative"of our invention produced in Example I.

THE INVENTION

It has now been discovered that novel solid and liquid foodstuff,chewing gum, medicinal product and toothpaste compositions and flavoringcompositions therefor having fruity/berry, pine needle-like aromas andsweet, fruity/berry, blueberry-like, pine needle-like, pine balsamflavor characteristics and novel perfume compositions, colognes andperfumed articles having sweet, berry, woody, piney, mint aroma noteswith a damascenone-like character and buttery and minty nuances, may beprovided by the utilization of the compound1-(3,3-dimethyl-2-norbornyl)-2-propanone having the structure: ##STR26##as the "endo" form or the "exo" form or a mixture of "endo" and "exo"forms.

The 1-(3,3-dimethyl-2-norbornyl)-2-propanone useful as indicated supramay be produced according to a process of reacting acetaldehyde withcamphene in the presence of a free radical initiator, as in the processset forth by Suga and Watanabe, Aust. Jour. of Chemistry, 20(9), 2033-6(1967) and Kheifits, et al, Zh. Org. Khim., 1969, 5(9) 1636-9. It canalso be produced by ultraviolet irradiation of acetaldehyde and camphenein the presence of an efficient hydrogen abstractor such as a1,2-diketone as set forth in Example I.

When the "norbornylpropanone derivative" of our invention is used as afood flavor adjuvant, the nature of the co-ingredients included withsaid "norbornylpropanone derivative" in formulating the productcomposition will also serve to alter, modify, augment or enhance theorganoleptic characteristics of the ultimate foodstuff treatedtherewith.

As used herein in regard to flavors, the terms "alter", "modify" and"augment" in their various forms mean "supplying or imparting flavorcharacter or note to otherwise bland, relatively tasteless substances oraugmenting the existing flavor characteristic where a natural flavor isdeficient in some regard or supplementing the existing flavor impressionto modify its quality, character or taste".

The term "enhance" is used herein to mean the intensification of aflavor or aroma characteristic or note without the modification of thequality thereof. Thus, "enhancement" of a flavor or aroma means that theenhancement agent does not add any additional flavor note.

As used herein, the term "foodstuff" includes both solid and liquidingestible materials which usually do, but need not, have nutritionalvalue. Thus, foodstuffs include soups, convenience foods, beverages,dairy products, candies, vegetables, cereals, soft drinks, snacks andthe like.

As used herein, the term "medicinal product" includes both solids andliquids which are ingestible non-toxic materials which have medicinalvalue such as cough syrups, cough drops, aspirin and chewable medicinaltablets.

The term "chewing gum" is intended to mean a composition which comprisesa substantially water-insoluble, chewable plastic gum base such aschicle, or substitutes therefor, including jelutong, guttakay, rubber orcertain comestible natural or synthetic resins or waxes. Incorporatedwith the gum base in admixture therewith may be plasticizers orsoftening agents, e.g., glycerine; and a flavoring composition whichincorporates the "norbornylpropanone derivative" of our invention, andin addition, sweetening agents which may be sugars, including sucrose ordextrose and/or artificial sweeteners such as cyclamates or saccharin.Other optional ingredients may also be present.

Substances suitable for use herein as co-ingredients or flavoringadjuvants are well known in the art for such use, being extensivelydescribed in the relevant literature. It is a requirement that any suchmaterial be "ingestibly" acceptable and thus non-toxic and otherwisenon-deleterious particularly from an organoleptic standpoint whereby theultimate flavor and/or aroms of the consumable material used is notcaused to have unacceptable aroma and taste nuances. Such materials mayin general be characterized as flavoring adjuvants or vehiclescomprising broadly stabilizers, thickeners, surface active agents,conditioners, other flavorants and flavor intensifiers.

Stabilizer compounds include preservatives, e.g., sodium chloride;antioxidants, e.g., calcium and sodium ascorbate, ascorbic acid,butylated hydroxy-anisole (mixture of 2- and3-tertiary-butyl-4-hydroxy-anisole), butylated hydroxy toluene(2,6-di-tertiary-butyl-4-methyl phenol), propyl gallate and the like andsequestrants, e.g., citric acid.

Thickener compounds include carriers, binders, protective colloids,suspending agents, emulsifiers and the like, e.g., agar agar,carrageenan; cellulose and cellulose derivatives such as carboxymethylcellulose and methyl cellulose; natural and synthetic gums such as gumarabic, gum tragacanth; gelatin, proteinaceous materials; lipids;carbohydrates; starches, pectines, and emulsifiers, e.g., mono- anddiglycerides of fatty acids, skim milk powder, hexoses, pentoses,disaccharides, e.g., sucrose corn syrup and the like.

Surface active agents include emulsifying agents, e.g., fatty acids suchas capric acid, caprylic acid, palmitic acid, myristic acid and thelike, mono- and diglycerides of fatty acids, lecithin, defoaming andflavor-dispersing agents such as sorbitan monostearate, potassiumstearate, hydrogenated tallow alcohol and the like.

Conditioners include compounds such as bleaching and maturing agents,e.g., benzoyl peroxide, calcium peroxide, hydrogen peroxide and thelike; starch modifiers such as peracetic acid, sodium chlorite, sodiumhypochlorite, propylene oxide, succinic anhydride and the like, buffersand neutralizing agents, e.g., sodium acetate, ammonium bicarbonate,ammonium phosphate, citric acid, lactic acid, vinegar and the like;colorants, e.g., carminic acid, cochineal, tumeric and curcuma and thelike; firming agents such as aluminum sodium sulfate, calcium chlorideand calcium gluconate; texturizers, anti-caking agents, e.g., aluminumcalcium sulfate and tribasic calcium phosphate; enzymes; yeast foods,e.g., calcium lactate and calcium sulfate; nutrient supplements, e.g.,iron salts such as ferric phosphate, ferrous gluconate and the like,riboflavin, vitamins, zinc sources such as zinc chloride, zinc sulfateand the like.

Other flavorants and flavor intensifiers include organic acids, e.g.,acetic acid, formic acid, 2-hexenoic acid, benzoic acid, n-butyric acid,caproic acid, caprylic acid, cinnamic acid, isobutyric acid, isovalericacid, alpha-methyl-butyric acid, propionic acid, valeric acid,2-methyl-2-pentenoic acid, and 2-methyl-3-pentenoic acid; ketones andaldehydes, e.g., acetaldehyde, acetophenone, acetone, acetyl methylcarbinol, acrolein, n-butanal, crotonal, diacetyl, 2-methyl butanal,beta, beta-dimethyl-acrolein, methyl-n-amyl ketone, n-hexenal,2-hexenal, isopentanal, hydrocinnamic aldehyde, cis-3-hexenal,2-heptanal, nonyl aldehyde, 4-(p-hydroxyphenyl)-2-butanone,alpha-ionone, beta-ionone, methyl-3-butanone, benzaldehyde, damascone,damascenone, acetophenone, 2-heptanone, o-hydroxyacetophenone,2-methyl-2-hepten-6-one, 2-octanone, 2-undecanone, 3-phenyl-4-pentenal,2-phenyl-2-hexenal, 2-phenyl-2-pentenal, furfural, 5-methyl furfural,cinnamaldehyde, beta-cyclohomocitral, 2-pentanone, 2-pentenal andpropanal; alcohols such as 1-butanol, benzyl alcohol, 1-borneol,trans-2-buten-1-ol, ethanol, geraniol, 1-hexanal, 2-heptanol,trans-2-hexenol-1, cis-3-hexen-1-ol, 3-methyl-3-buten-1-ol, 1-pentanol,1-penten-3-ol, p-hydroxyphenyl-2 -ethanol, isoamyl alcohol, isofenchylalcohol, phenyl-2-ethanol, alpha-terpineol, cis-terpineol hydrate,eugenol, linalool, 2-heptanol, acetoin; esters, such as butyl acetate,ethyl acetate, ethyl acetoacetate, ethyl benzoate, ethyl butyrate, ethylcaprate, ethyl caproate, ethyl caprylate, ethyl cinnamate, ethylcrotonate, ethyl formate, ethyl isobutyrate, ethyl isovalerate, ethyllaurate, ethyl myristate, ethyl alpha-methylbutyrate, ethyl propionate,ethyl salicylate, trans-2-hexenyl acetate, hexyl acetate, 2-hexenylbutyrate, hexyl butyrate, isoamyl acetate, isopropyl butyrate, methylacetate, methyl butyrate, methyl caproate, methyl isobutyrate,alpha-methylphenylglycidate, ethyl succinate, isobutyl cinnamate,cinnamyl formate, methyl cinnamate and terpenyl acetate; hydrocarbonssuch as dimethyl naphthalene, dodecane, methyl diphenyl, methylnaphthalene, myrcene, naphthalene, octadecane, tetradecane, tetramethylnaphthalene, tridecane, trimethyl naphthalene, undecane, caryophyllene,1-phellandrene, p-cymene, 1-alphapinene; pyrazines such as2,3-dimethylpyrazine, 2,5-dimethylpyrazine, 2,6-dimethylpyrazine,3-ethyl-2,5-dimethylpyrazine, 2-ethyl-3,5,6-trimethylpyrazine,3-isoamyl-2,5-dimethylpyrazine, 5-isoamyl-2,3-dimethylpyrazine,2-isoamyl-3,5,6-trimethylpyrazine, isopropyl dimethylpyrazine, methylethylpyrazine, tetramethylpyrazine, trimethylpyrazine; essential oils,such as jasmine absolute, cassia oil, cinnamon bark oil, rose absolute,orris absolute, lemon essential oil, Bulgarian rose, yara yara andvanilla; lactones such as δ-nonalactone; sulfides, e.g., methyl sulfideand other materials such as maltol, acetoin and acetals (e.g.,1,1-diethoxy-ethane, 1,1-dimethoxyethane and dimethoxymethane).

The specific flavoring adjuvant selected for use may be either solid orliquid depending upon the desired physical form of the ultimate product,i.e., foodstuff, whether simulated or natural, and should, in any event,(i) be organoleptically compatible with the "norbornylpropanonederivative" of our invention by not covering or spoiling theorganoleptic properties (aroma and/or taste) thereof; (ii) benon-reactive with the "norbornylpropanone derivative" of our inventionand (iii) be capable of providing an environment in which the"norbornylpropanone derivative" can be dispersed or admixed to provide ahomogeneous medium. In addition, selection of one or more flavoringadjuvants, as well as the quantities thereof will depend upon theprecise organoleptic character desired in the finished product. Thus, inthe case of flavoring compositions, ingredient selection will vary inaccordance with the foodstuff, chewing gum, medicinal product ortoothpaste to which the flavor and/or aroma are to be imparted,modified, altered or enhanced. In contradistinction, in the preparationof solid product, e.g., simulated foodstuffs, ingredients capable ofproviding normally solid compositions should be selected such as variouscellulose derivatives.

As will be appreciated by those skilled in the art, the amount of"norbornylpropanone derivative" employed in a particular instance canvary over a relatively wide range, depending upon the desiredorganoleptic effects to be achieved. Thus, correspondingly, greateramounts would be necessary in those instances wherein the ultimate foodcomposition to be flavored is relatively bland to the taste, whereasrelatively minor quantities may suffice for purposes of enhancing thecomposition merely deficient in natural flavor or aroma. The primaryrequirement is that the amount selected to be effective, i.e.,sufficient to alter, modify or enhance the organoleptic characteristicsof the parent composition, whether foodstuff per se, chewing gum per se,medicinal product per se, toothpaste per se, or flavoring composition.

The use of insufficient quantities of "norbornylpropanone derivative"will, of course, substantially vitiate any possibility of obtaining thedesired results while excess quantities prove needlessly costly and inextreme cases, may disrupt the flavor-aroma balance, thus provingself-defeating. Accordingly, the terminology "effective amount" and"sufficient amount" is to be accorded a significance in the context ofthe present invention consistent with the obtention of desired flavoringeffects.

Thus, and with respect to ultimate food compositions, chewing gumcompositions, medicinal product compositions and toothpastecompositions, it is found that quantities of "norbornylpropanonederivative" ranging from a small but effective amount, e.g., 0.5 partsper million up to about 100 parts per million based on total compositionare suitable. Concentrations in excess of the maximum quantity statedare not normally recommended, since they fail to prove commensurateenhancement of organoleptic properties. In those instances, wherein the"norbornylpropanone derivative" is added to the foodstuff as an integralcomponent of a flavoring composition, it is, of course, essential thatthe total quantity of flavoring composition employed be sufficient toyield an effective "norbornylpropanone derivative" concentration in thefoodstuff product.

Food flavoring compositions prepared in accordance with the presentinvention preferably contain the "norbornylpropanone derivative" inconcentrations ranging from about 0.1% up to about 15% by weight basedon the total weight of the said flavoring composition.

The composition described herein can be prepared according toconventional techniques well known as typified by cake batters and fruitdrinks and can be formulated by merely admixing the involved ingredientswithin the proportions stated in a suitable blender to obtain thedesired consistency, homogeneity of dispersion, etc. Alternatively,flavoring compositions in the form of particulate solids can beconveniently prepared by mixing the "norbornylpropanone derivative"with, for example, gum arabic, gum tragacanth, carrageenan and the like,and thereafter spray-drying the resultant mixture whereby to obtain theparticular solid product. Pre-prepared flavor mixes in powder form,e.g., a fruit-flavored powder mix are obtained by mixing the dried solidcomponents, e.g., starch, sugar and the like and the "norbornylpropanonederivative" in a dry blender until the requisite degree of uniformity isachieved.

It is presently preferred to combine with the "norbornylpropanonederivative" of our invention, the following adjuvants:

p-Hydroxybenzyl acetone;

Geraniol;

Cassia Oil;

Acetaldehyde;

Maltol;

Ethyl methyl phenyl glycidate;

Benzyl acetate;

Dimethyl sulfide;

Eugenol;

Vanillin;

Caryophyllene;

Methyl cinnamate;

Guiacol;

Ethyl pelargonate;

Cinnamaldehyde;

Methyl anthranilate;

5-Methyl furfural;

Isoamyl acetate;

Isobutyl acetate;

Cuminaldehyde;

Alpha ionone;

Cinnamyl formate;

Ethyl butyrate;

Methyl cinnamate;

Acetic acid;

Gamma-undecalactone;

Naphthyl ethyl ether;

Diacetyl;

Furfural;

Ethyl acetate;

Anethole;

2,3-Dimethyl pyrazine;

2-Ethyl-3-methyl pyrazine;

3-Phenyl-4-pentenal

2-Phenyl-2-hexenal;

2-Phenyl-2-pentenal;

3-Phenyl-4-pentenal diethyl acetal;

Beta-damascone (1-crotonyl-2,2,6-trimethylcyclohex-1-one)

Damascenone (1-crotonyl-2,2,6-trimethylcyclohexa-1,5-diene);

Beta-cyclohomocitral (2,2,6-trimethylcyclohex-1-ene carboxaldehyde);

Isoamyl butyrate;

Cis-3-hexenol-1;

2-Methyl-2-pentenoic acid;

Elemecine (4-allyl-1,2,6-trimethoxy benzene;

Isoelemecine (4-propenyl-1,2,6-trimethoxy benzene; and

2-(4-Hydroxy-4-methylpentyl) norbornadiene prepared according to U.S.Application for Letters Patent Ser. No. 461,703, filed on Apr. 17, 1974.

The "norbornylpropanone derivative" and one or more auxiliary perfumeingredients, including, for example, alcohols, aldehydes, nitriles,esters, cyclic esters and natural essential oils, may be admixed so thatthe combined odors of the individual components produce a pleasant anddesired fragrance, particularly and preferably in woody and/or pineyfragrances. Such perfume compositions usually contain (a) the main noteor the "bouquet" or foundation stone of the composition; (b) modifierswhich round off and accompany the main note; (c) fixatives which includeodorous substances which lend a particular note to the perfumethroughout all stages of evaporation and substances which retardevaporation; and (d) topnotes which are usually low boiling freshsmelling materials.

In perfume compositions, it is the individual components whichcontribute to their particular olfactory characteristics, however, theover-all sensory effect of the perfume composition will be at least thesum total of the effects of each of the ingredients. Thus, the"norbornylpropanone derivative" of our invention can be used to alter,modify or enhance the aroma characteristics of a perfume composition,for example, by utilizing or moderating the olfactory reactioncontributed by another ingredient in the composition.

The amount of "norbornylpropanone derivative" of our invention whichwill be effective in perfume compositions as well as in perfumedarticles and colognes depends on many factors, including the otheringredients, their amounts and the effects which are desired. It hasbeen found that perfume compositions containing as little as 0.01% of"norbornylpropanone derivative" or even less (e.g., 0.005%) can be usedto impart a sweet, berry, woody, piney, minty aroma withdamascenone-like nuances to soaps, cosmetics or other products. Theamount employed can range up to 70% of the fragrance components and willdepend on considerations of cost, nature of the end product, the effectdesired on the finished product and the particular fragrance sought.

The "norbornylpropanone derivative" of our invention is useful [takenalone or together with other ingredients in perfume compositions] as(an) olfactory component(s) in detergents and soaps, space odorants anddeodorants, perfumes, colognes, toilet water, bath preparations, such aslacquers, brilliantines, pomades and shampoos; cosmetic preparations,such as creams, deodorants, hand lotions and sun screens; powders, suchas talcs, dusting powders, face powders and the like. When used as (an)olfactory component(s) as little as 1% of the "norbornylpropanonederivative" of our invention will suffice to impart an intense sweet,berry, woody, piney, minty aroma with damascenone-like nuances to woodyand/or piney and/or herbal formulations. Generally, no more than 3% ofthe "norbornylpropanone derivative" of our invention, based on theultimate end product, is required in the perfume composition.

In addition, the perfume composition or fragrance composition of ourinvention can contain a vehicle, or carrier for the "norbornylpropanonederivative". The vehicle can be a liquid such as an alcohol, a non-toxicalcohol, a non-toxic glycol, or the like. The carrier can also be anabsorbent solid, such as a gum (e.g., gum arabic) or components forencapsulating the composition (such as gelatin).

It will thus be apparent that the "norbornylpropanone derivative" of ourinvention can be utilized to alter, modify or enhance sensoryproperties, particularly organoleptic properties, such as flavor(s)and/or fragrance(s) of a wide variety of consumable materials.

The following Examples serve to illustrate our invention and thisinvention is to be considered restricted thereto only as indicated inthe appended claims.

All parts and percentages given herein are by weight unless otherwisespecified.

EXAMPLE I PREPARATION OF 1-(3,3-DIMETHYL-2-NORBORNYL)-2-PROPANONE

A 1 liter water jacketed photochemical reaction vessel equipped withmagnetic stirrer and pyrex immersion well is charged with 418 g camphene(807, Aldrich) and 372 g acetaldehyde and 30 g diacetyl (photochemicalhydrogen abstractor). The mixture is irradiated with a 450 mediumpressure mercury lamp (Hanovia) for 55 hours, during which time five 30g portions of diacetyl are added at varying intervals. The reactionmixture is combined with 150 g of 1,2,4-trimethyl benzene and washedwith water. The material is distilled without fractionation and thenredistilled through a 5 foot Vigreux column to yield 224 g colorlessproduct, b.p. 70°-72° (55 mm Hg).

The NMR spectrum is as follows:

    ______________________________________                                        δ ppm      Assignment                                                   ______________________________________                                        0.74 (s, 3H)     gem dimethyl protons                                         0.99 (s, 3H)                                                                  1.15-2.0 (m, 7H)                                                                                ##STR27##                                                   2.08 (s, 3H)                                                                                    ##STR28##                                                   2.40 (d, J=7Hz, 2H)                                                                             ##STR29##                                                   ______________________________________                                    

the Infrared data is as follows:

2960, 1717, 2885 cm⁻¹

The Mass Spectral data is as follows:

m/e 43, 111, 41, 122, 39, 67

The NMR spectrum is set forth in FIG. 1. The Infrared spectrum is setforth in FIG. 2.

EXAMPLE II FLAVOR FORMULATION USING THE MATERIAL PRODUCED IN EXAMPLE I

The following mixture is prepared:

    ______________________________________                                        Ingredient            Parts by Weight                                         ______________________________________                                        Para-hydroxy benzyl acetone                                                                         5                                                       Vanillin              2                                                       Maltol                3                                                       Alpha-Ionone (1% solution in                                                  propylene glycol)     15                                                      Isobutyl Acetate      15                                                      Ethyl Butyrate        5                                                       Ethyl Acetate         5                                                       Dimethyl Sulfide (10% solution                                                in propylene glycol)  5                                                       Acetic acid           15                                                      Acetaldehyde          20                                                      Propylene Glycol      910                                                     1-(3,3-dimethyl-2-norbornyl)-                                                 2-propanone produced in Example I                                                                   3                                                       ______________________________________                                    

When 1-(3,3-dimethyl-2-norbornyl)-2-propanone is added to the aboveformulation it adds an excellent raspberry kernel character causing theformulation to be much more natural in taste and aroma. The formulationis preferred over the same formulation not containing the1-(3,3-dimethyl-2-norbornyl)-2-propanone.

EXAMPLE III

A perfume composition is prepared by admixing the following ingredientsin the indicated proportions:

    ______________________________________                                        Ingredient          Amount (Grams)                                            ______________________________________                                        n-Decyl Aldehyde    1                                                         n-Dodecyl Aldehyde  2                                                         Methyl Nonyl Acetaldehyde                                                                         0.5                                                       Linalool            50                                                        Linalyl Acetate     70                                                        Phenyl Ethyl Alcohol                                                                              100                                                       Petigrain SA        20                                                        Bergamot Oil        30                                                        Alpha Methyl Ionone 25                                                        1-(3,3-dimethyl-2-norbornyl)-                                                 2-propanone produced according                                                to Example I        10                                                        Cyclized Bicyclo C-12 material                                                produced according to the                                                     Process of Example IV of                                                      Canadian Patent 854,225,                                                      issued on October 20, 1970                                                                        5                                                         Isobornyl cyclohexyl alcohol                                                                      10                                                        Benzyl Acetate      25                                                        2-n-Heptyl cyclopentanone                                                                         5                                                                             353.3 (TOTAL)                                             ______________________________________                                    

The foregoing blend is evaluated and found to have a high degree ofrichness and persistence in its novel natural piney quality. This basecomposition can be admixed with aqueous ethanol, chilled and filtered toproduce a finished cologne. The cologne so prepared has a sweet, berry,woody, piney, mint aroma note with a damascenone-like character andbuttery and minty nuances. The base composition can also be used toscent soap or other toilet goods such as lotions, aerosols, sprays andthe like.

EXAMPLE IV PREPARATION OF A COSMETIC-POWDER COMPOSITION

A cosmetic powder is prepared by mixing in a ball mill, 100 g of talcumpowder with 0.25 g of 1-(3,3-dimethyl-2-propanone prepared according toExample I. It has an excellent sweet, berry, woody, piney, mint aromawith a damascenone-like character and buttery and minty nuances.

What is claimed is:
 1. A process for augmenting or enhancing the flavorof a foodstuff comprising the steps of adding to a foodstuff from 0.5parts per million up to about 100 parts per million of compound havingthe structure ##STR30## wherein the wavy lines are representative of exoor endo configurations.
 2. A flavor modifying composition comprisingfrom about 0.1% up to about 15% by weight based on the total weight offlavoring composition of a compound having the structure wherein thewavy lines are representative of exo or endo configurations: ##STR31##the remainder of said composition being an adjuvant selected from thegroup consisting of p-hydroxybenzyl acetone, maltol, benzyl acetate,methyl cinnamate, geraniol, ethyl methyl phenyl glycidate, vanillin,methyl anthranilate, alphaionone, gamma undecalactone, ethylpelargonate, isoamyl acetate, acetaldehyde, dimethyl sulfide, isobutylacetate, acetic acid, ethyl butyrate, diacetyl, anethole,cis-3-hexenol-1, naphthyl ethyl ether, ethyl acetate, isoamyl butyrate,2-methyl-2-pentenoic acid, 2(4-hydroxy-4-methylphenyl) norbornadiene,4-allyl-1,2,6-trimethoxy benzene, cassia oil, eugenol, caryophyllene,guiacol, cinnamaldehyde, 5-methyl furfural, cuminaldehyde, cinnamylformate, methyl cinnamate, furfural, 2,3-dimethyl pyrazine,2-ethyl-3-methyl pyrazine, 3-phenyl-4-pentenal, 2-phenyl-2-hexenal,2-phenyl-2-pentenal, 3-phenyl-4-pentenal diethyl acetal,1-crotonyl-2,2,6-trimethylcyclohex-1-ene,1-crotonyl-2,2,6-trimethylcyclohexa-1,5-diene,2,2,6-trimethyl-cyclohex-1-ene carboxaldehyde and4-propenyl-1,2,6-trimethoxy benzene.